Method for the preparation of copolymers of the polysulfonic type and compounds resulting therefrom



United States Patent 3,385,838 METHGD FQR THE PREPARATEQN F C(EPULY- MERS GE THE ROLYSULFQNEC TYPE AND CUM- PDUNDS RESULTENG THEREFRQh'i Georgette Steinbach-van Gaver, Paris, France, assign-0r to llroduits Chimiques Pechiney-Saint-Gobain, Neuillystir-Seine, France No Drawing. Filed .Ian. 12, 1965, Ser. No. 425,063 Claims priority, application France, Jan. 15, 1964,

cil,416 it} Claims. (Cl. 269-193) ABSTRACT 6F THE DECLOSURE Polysulphonic copolymers and a method for their production, the polymerization involving the known mixture of sulphurous anhydride, at least one unsaturated hydrocarbon of the alkene type, and at least one other unsaturated compound. The improved method producing the improved compounds involves copolymerization in the presence of an organic derivative of a metalloid selected from the group consisting of an aliphatic nitrated compound, aliphatic mercaptans, unsaturated organic sulphur compounds, and organic halogenated compounds.

SPECIFICATION This invention relates to a method for the preparation of copolymers of the polysulphonic type and to compounds resulting therefrom.

It has previously been reported that copolymers of the polysulphonic type can be prepared on the basis of an unsaturated hydrocarbon, and of sulfurous anhydride, associated in substantially equimolecular proportions. These copolymers constitute thermoplastic compounds, however, the industrial applications of these compounds are limited, due to the fact that they have an insufficient thermal stability. It is also known that it is possible to improve the properties of these types of compounds, to a limited degree, by associating the following within a molecule of the interpolymer type: an unsaturated hydrocarbon, sulfurous anhydride and a third monomer, constituted by another unsaturated organic compound, usually called termonomer.

Although certain one of the copolymers so prepared have interesting properties, it has now been found that it is possible to obtain polymer compounds of the polysulphonated type. Such compounds have properties which are substantially improved when compared to the presently available types.

It is a general object of this invention to provide polymer compounds of the polysulphonated types having properties which significantly increase the utility of the compounds.

It is a more specific object of this invention to provide an improved method for the preparation of compounds of the type set forth in the foregoing object.

These and other objects of this invention will appear hereinafter and it will be understood that the specific examples hereinafter set forth are provided primarily for purposes of illustrating the invention and not for the purpose of limiting the invention.

According to the present invention copolymers of the polysulphonated type are prepared by copolymerization of sulfurous anhydride, of at least one unsaturated hydrocarbon and of one other unsaturated organic compound.

The unsaturated hydrocarbon may be an alkene of the general formula C I-I wherein n is greather than 2. The other unsaturated organic compound may comprise acrylonitrile introduced into molecular proportions be low 0.5 with respect to the unsaturated hydrocarbon employed.

The copolymerization is effected in the presence of an organic derivate of a metalloid selected from the groups V, V I and VIIa of the periodic classification of elements. Preferably polymerization is carried out in the presence of an organic derivate of nitrogen, an organic derivate of sulfur or an organic halogenated derivate.

Among the organic nitrogen compounds which are used to good advantage in the method of this invention, the aliphatic nitrated compounds of the formula C H NO used in such a manner that the molecular ratio of the nitrogen compound with the total of the unsaturated compounds used is preferably between .1 and 1 percent, are particularly suitable.

With respect to suitable organic sulfur derivatives for the method of this invention, the aliphatic mercaptans of the general formula C H SI-i, n being between 6 and 20, and also the sulfides of the unsaturated organic compounds such as allyl and vinyl sulfides, are highly satisfactory.

These organic sulphur derivatives are used in amounts such that the molecular ratio of the organic sulphur compound to the total of the unsaturated organic compounds used is preferably between .01 and 5 percent.

Particularly suitable for use as the halogenated organic derivates in the method of this invention are allyl bromide, bromoform, iodoform, carbon tetrachloride, trichlorethylene, ethyl bromo malonate, benzene-sulfonyl chloride and chloracetaldehyde. These halogenated organic compounds are so used that their molecular ratio to the total of the unsaturated compounds used is preferably between .01 and 2 percent.

It is also preferable to employ in the reaction such a quantity of sulfurous anhydride that the molecular ratio of the sulfurous anhydride to the unsaturated organic compounds used is between 1 and 2. The copolymerization of the monomer compound defined above involves generally the use of conventional techniques and is usually carried out in the presence of a polymerization catalyst. in practice, the copolymerization is carried out at a temperature generally below C., and preferably between 30 and 60 C. The operation generally lasts from 4 to 20 hours.

The copolymers prepared according to this invention possess considerably improved properties when compared to the copolymer compounds on the basis of unsaturated compounds and sulfurous anhydride prepared according to prior art. The technical progress achieved is great, in view of the fact that certain of these properties, such as the heat stability, the fluidity of the melted copolymers, and the transparency of the shaped objects, make it possible to expand considerably the possible applications of these compounds. The products so prepared are suitable for use in many applications now using thermoplastic compounds. They can be used to good advantage in a large number of industrial applications such as those originating from molding, injection and drawing in fibers.

The following examples will illustrate the method of the invention:

EXAMPLE 1 The following provides an illustration of a system wherein the copolymerization was carried out in an emulsion of butene-l, sulfurous anhydride and acrylonitrile in the presence of tertiododecyl mercaptan. The following ingredients were introduced successively at room temperature into a glass reactor which is provided with a mechanical agitator and a water circulation heating 4 tifier or stabilizer, at a pressure of 1,200 kg./cm. The sample obtained was perfectly transparent and free from bubbles.

Water ml 300.000 Ammonium nitrate acting as copolymcrization For the purpose of comparison, the followmg table catalyst "grams" 5 hS S the vlscositles and losses of we1ght at 194 C. meas- Ammonium alkyl sulfonate, acting as l i. ured on copolymers prepared according to Example 1 as fi 9 Well as the same measurements made on two copolymers 1 at 95 percent Purity d 2090 prepared according to prior art. Of the prior art illuss lf r anhydride d 152 trated, reference A is based on butene-l and sulfurous an- Acrylonitrile ..d0 1 8.560 10 hydride, and reference B is based on butene-l, sulfurous Tertiododecyl mercaptan do 3.700 anhydride and acrylonitrile.

TABLE I Aerylo- Tertio- Intrinsic Percent of loss in Butene l, S02, (15.) nitrile, dodeeylviscosity, weight at 194 0.

(g) (g.) mercaptan, (g.)

(g.) 1 hr. 2 hr. 3 hr.

82 152 100 22 32 40 B 82 152 18.56 45 12 23 Examplel 82 152 18.56 3.7 as 4.5 8 12 Under stirring the temperature of the reaction milieu This table shows particularly clearly that the copolymer increased to 48 C. with the pressure being about 9 kg./ prepared according to the invention has, with relation 0111 The operation was continued at 48 C. for 6 hours 25 to the control copolymers provided for comparison, a and at the end of the operation the pressure was brought much lower viscosity and weight loss at 194 C. down to 2 kg./cm. After degasification of the monomers Furthermore, the prior art copolymers were subjected which did not react, the copolymer emulsion was introto the molding test by injection and, even when operatduced into a solution of 15 grams of calcium chloride in ing at the lowest possible temperature, they have very 300 ml. of water at 50 C. The flocculated copolymer serious drawbacks (bubbles, coloration) originating from was filtered, washed in water until the washing water had a considerable degradation.

:1 pH of 5, and it was then dried at 50 C. in an air cir- For purposes of further comparison Table II lists the culation stove. The end product comprised 163 grams viscosities and losses of weight at 194 0, measured on (that is a transformation ratio of 87 percent with regard a copolymer prepared according to Example 2 as well to butene-l) of a copolymer having a centesimal analysis as the same measurements taken on the two copolymers as follows: of the prior art shown in Table I.

TABLE II Aerylo- Lauryl Intrinsic Percent of loss in Butane-1, S01, nitrilc, mercaptan, viscosity, weight at 194 C.

1hr. 2hr1 3hr.

A 82 152 100 22 32 13 82 152 18. 56 12 21 23 Example 82 152 18.56 3.7 35 c 10 13 Percent EXAMPLE 2 Carbon This example illustrates the method of this invention Hydrogen 5 wherein the copolymerization was effected in an emulslilfur sion of butene-l, sulfurous anhydride and aerylonitril Nltfogen in the presence of lauryl mercaptan.

The intrinsic viscosity of the copolymer was also meas- Operation carried out the Same Pondition as ured in tetrahydrofurane (.6 gram of copolymer per 100 m t Precedmg example With the excePtlon that the ml. of solvent at 25 C.). The viscosity measured under tertlododecyl mercaptan was replaced with grams these conditions was 36 cc /gram of lauryl mercaptan. 140 grams of dry copolymer were Finally, the heat stability of the copolymer wa meas. obtalned, corresponding to a rate of transformation ured by means of a thermoscale of the MacBain type. A of Sample of 15 mg of copolymer in power f was The centesimal analysis of the product was as follows: jected to heating at 194 C. under an air current and the relative loss of weight was determined at the end of 1, 2 Percent and 3 hours of treatment. These losses in weight were Carbon 42-15 4.5, 8, and 12 percent, respectively. Hydrogen The flow speed of the copolymers obtained with an i 26-30 apparatus designed in accordance with ASTM D123'8- 65 Nltr'ogen 57T standard was also measured. The product was intro- The intrinsic viscosity of the copolymer in solution in duced in powder form into a steel cylinder heated to a tetrahydrofurane was 35 cc./gram and the losses of constant temperature of 150 C. A piston moving in the weight at 194 C. were 6, '10 and 13%, respectively, cylinder applied a load of 10.463 kgs. and forced the after 1, 2 and 3 hours. The speed of flow, measured melted copolymer to flow across a draw plate with a diunder the conditions described in Example 1 was ameter of 2 mm. and a length of 8 mm. At regular inter- .327 g./min. vals the mass of product discharged was measured and The molding test by injection of copolymer which was the flow speed, expressed in g./min., was .325. The coneither plastified nor stabilized produced favorable rcpolymer thus prepared was then subjected to a molding suits as with the copolymer prepared according to test by injection at 200 0., without introducing any plas- Example 1.

Table II shows clearly that the copolymers prepared according to the invention have, with relation to the control copolymers mentioned for comparisons sake, a much lower viscosity and loss of weight at 194 C.

EXAMPLE 3 The centesimal composition of the product obtained was as follows:

Percent Carbon 42 Hydrogen 6:4 Sulfur 26.2 Nitrogen 2.0

Bromine, less than .l%.

The viscosity of the copolymer in solution in tetrahydrofurane was 27 cc./gram and the losses in weight at 194 C. were 5, 10 and percent, respectively, after 1, '2 and 3 hours. The flow speed was .343 gram/min.

The molding test by injection of copolymer which was neither plastified nor stabilized, produced results favorably comparable to the results achieved with the polymer prepared according to Example 1.

For purposes of comparison, Table 111 lists the visc-osities and losses of weight measured on the copolymer prepared according to Example 3 and the same measurements taken on the two prior art copolymers identified above in Example 1.

194 C. was 4, 7.9, and 10 percent, respectively, after 1, -2 and 3 hours. The flow speed under the conditions of Example 1 was .325 g./min.

The molding test by injection of the crude copolymer produced results which compared favorably with the tests on the copolymer prepared according to Example 1.

It will be understood that various changes and modifications may be made in the method of this invention as well as in the novel compounds produced by the method which provides the characteristics of the invention without departing from the spirit thereof particularly as defined in the following claims.

That which is claimed is:

1. In a method for the preparation of copolymers of the polysulphonic type wherein there is first provided a mixture of sulfurous anhydride, at least one unsaturated hydrocarbon of an alkene type having the general formula C H with n being greater than 2, and one other unsaturated organic compound, and thereafter copolymerizing said mixture at a temperature less than 100 C., the improvement wherein the copolymerization is carried out in the presence of an organic derivative selected from the group consisting of (a) an aliphatic mercaptan having the formula C H SH, n being between 6 and 20,

(b) an aliphatic nitrated derivative having the formula CH MD Q,

(c) an unsaturated organic sulfur compound selected from the group comprising allyl sulfide and vinyl sulfide,

(d) and an organic halogenated compound selected from the group comprising allyl bromide, bromoform, iodoform, carbon tetrachloride, trichlorethylene, ethyl bromomalonate, benzene sulfonyl chloride and chloracetaldehyde.

TABLE III Acrylo- Allyl Intrinsic Percent of loss of Butene1, S02, nitrile, Brtzmgde, Vis(c0s)1ty, weight at 194 C.

(g) (g) g 1hr. 2hr. 3hr.

This table clearly shows that the copolymers prepared according to this invention is characterized with regard to the control copolymers mentioned for comparisons sake, by a much lower viscosity and loss of weight at 194 C.

EXAMPLE 4 In this example the copolymerization is undertaken in an emulsion of butene-l, sulfurous anhydride and acrylonitrile in the presence of tertiododecyl mercaptan, using an autoclave of 10 liters. The following ingredients were introduced into the glass autoclave:

The operation was carried out under the same conditions as in Example 1 and 1590 grams of dry copolymer were obtained, corresponding to a rate of transformation of 85%. The centesimal analysis of the product was as follows:

Percent Carbon 4 1.2 Hydrogen 6.3 Sulfur 25.2 Nitrogen 1.4

The viscosity of the copolymer in solution in tetrahydrofurane was 35 cc./ gram and the loss of weight at 2. A method in accordance with claim 1 wherein the molecular ratio of the aliphatic mercaptan to the unsaturated organic compounds is between 0.01 and 5.0 percent.

3. A method in accordance with claim 1 wherein the molecular ratio of the organic derivative compared to the unsaturated organic compounds is between 0.1 and 1.0 percent.

4. A method in accordance with claim 1 wherein the molecular ratio of the organic sulfur compound compared to the unsaturated organic compounds is between 0.1 and 5.0 percent.

5. A method in accordance with claim 1 wherein the molecular ratio of the halogenated organic compound compared to the total of the unsaturated organic compounds is between 0.01 and 2.0 percent.

6. A method in accordance with claim 1 wherein the molecular ratio of the sulfurous anhydride to the organic unsaturated compounds is between 1.0 and 2.0.

7. A method in accordance with claim 1 wherein the said other unsaturated organic compound comprises acrylonitrile and is employed in a molecular proportion of less than 0.5 with respect to the unsaturated hydrocarbon.

8. A method in accordance with claim 1 wherein the copolymerization is carried out between 30 and 60 C.

9. A method in accordance with claim 1 wherein the duration of operation of the copolymerization is between 4 and 20 hours.

10. In a composition of matter comprising copolymers of sulfurous anhydride, at least one unsaturated hydrocarbon of an alkene type having the general formula 7 8 C H with n being greater than 2 and one other unform, iodoform, carbon tetrachloride, trichloroethylsaturated organic compound comprising acrylonitrile, the ene, ethylbromomalonate, benzene sulfonyl chloride improvement wherein said composition contains at least and chloracetaldehyde. gigs 0ofrganic derivative selected from the group consist- 5 References Cited (a) an aliphatic mercaptan having the formula UNITED STATES PATENTS C H SH, n being between 6 and 20, (b) an aliphatic nitrated derivative having the formula E21 z' f' CHHQMDNOZ 2,606,169 8/1952 =Roney 26079.3 (c) an unsaturated organlc sulfur compound selected 10 2,705,227 3/1955 Stamatotf 2604595 from the group comprising allyl sulfide and vinyl 2,765,295 10/1956 Crouch aL sulfide,

(d) and an organic halogenated compound selected JOSEPH SCHOFER, Primary Examinerfrom the group comprising allyl bromide, bromo- D. K. DENENBERG, Assistant Examiner. 

